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Title: Site-Selective Probes of Mixed-Node Metal Organic Frameworks for Photocatalytic Hydrogen Generation

Journal Article · · Journal of Physical Chemistry. C

Metal organic frameworks (MOFs) have emerged as a novel platform offering new promise for photocatalytic applications. In this work, we report a mixed-node MOF (MOF-74) based on earth-abundant metals (i.e., Co and Fe) as highly active and robust photocatalysts for visible light-driven H2 generation. Using in situ X-ray absorption spectroscopy which allows us to selectively probe the individual metal node in MOFs, we unambiguously identified the catalytic active sites and captured the key intermediate species under the standard catalytic conditions. We show that both Co and Fe centers in MOF-74 are the reversible active sites, and the accumulation of their reduced states is responsible for the observed induction period for H2 generation. Moreover, we captured the key intermediate species formed when the reaction reaches equilibrium, which is featured by an elongated Co–O bond at the Co center and a more distorted octahedral geometry at the Fe center with respect to their original geometry. These results not only demonstrate the potential of MOF-74 as a single site catalyst for H2 generation but also provide new insight into the catalytic mechanism for further development.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Petroleum Research Fund (PRF); Wuyi University
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1595943
Journal Information:
Journal of Physical Chemistry. C, Vol. 124, Issue 2; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 14 works
Citation information provided by
Web of Science

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